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SOAPS AND DETERGENTS

(K. R. JANARDHANAN)
In olden days clothes were cleaned by beating them on rocks in the nearest
stream. This practice is followed even today in many villages. Sometimes plants
such as soap nuts are used as cleaning agents. Such plants contain saponins,
chemical compounds that produce a soapy lather. These saponins were probably
the first detergents used.
History :

Ashes of plants contain potassium carbonate (K2 Co3) and

sodium carbonate (Na2 Co3). The carbonate ion present in both these compounds,
reacts with water to form an alkaline solution. The basic solution has detergent
properties. These alkaline plant ashes were used as cleaning agents by the earliest
civilizations at least 4000 years ago. Europeans were using plant ashes to wash
their clothes as recently as 100 years ago. Sodium carbonate is still sold as washing
soda and is being used for cleansing purposes. The discovery of disease causing
micro organisms and subsequent public health practices brought about an increased
interest in cleanliness by the late eighteenth century. Soap was in common use by
the middle of the nineteenth century.
The first written record of soap can be seen in the writings of the Roman pliny the
Elder. He described the Phoenicians synthesis of soap by using goat tallow and
ashes. By the second centaury A. D, sodium carbonate was heated with time (from
limestone) to produce sodium hydroxide (lye). The sodium hydroxide was heated
with animal fats or vegetable oils to produce soap. Other societies made soap in
much the same manner.
The large scale manufacture of soap was not possible until the discovery of
practical methods of manufacturing alkalies on a large scale. This did not take

place until about 1800. Soaps are compounds formed by the reaction of bases with
fats, chemically known as fatty acid esters. The most important fatty acid esters.
The three most important fatty acid esters are
Palmitin [( C15 H3 1 COO)3 C3 H5)
Stearin [( C17 H35 COO)3 C3 H5)
and
Olein [( C17 H3 3 COO)3 C3 H5)
They are found in lard, tallow, olive oil, cotton seed oil, and other animal and
vegetable fats or oils. Soap is usually made by the reaction of animal fat or
vegetable oil with sodium hydroxide. The process of treating fats with bases or
alkalies is called Saponification. Vegetable oils, with unsaturated carbon chains,
produce soft soaps. Animal fats yield hard soaps. Coconut oils with shorter carbon
chains, yield soaps that are more soluble in water.
Soap to day :

In modern commercial soap making, the fats and oils are often

hydrolysed with super heated steam. The fatty acids then are neutralized to make
soap. The process takes place in large cylindrical vessel. The next step in the
manufacture of soap is called graining or Saltingout. This involves the addition of
common salt (NaCl). During this process the soap becomes insoluble in brine and
separates from the solution. The soap may be washed several times with brine to
rid it of free alkali.
The molten soap may be run into large frames from which bars may be cut, or it
may be run over cold rollers, producing thin sheets which are scraped to form soap
chips. The molten soap may also be squirted from a nozzle as a spray into hot air to
form powdered soap.

All ingredients except moisture should be declared. All of them should be noninjurious to skin.
Why bathing bars:
Bathing bars were introduced in India in 1985, when the country was facing
acute scarcity of vegetable cooking oils. Much of the vegetable oils were being
used by industry. The government started importing palmoil from abroad. In order
to control the use of vegetable oils for soap making, the government allowed the
manufacturers of soap to introduce bathing bars. The introduction of bathing bars
reduced the use of cooking oils for soap making. Thus more cooking oil became
available for domestic use. The price of bathing bars were determined according to
the total fatty matter contained in them and more importantly the type of fatty
matter used. Due to this step government could reduce the quantum of import of
vegetable oil and could save a lot of foreign exchange.
Types of bathing bars
There are two types of bathing bars (1) made up of partial soap and partial
synthetic detergent (syndet).

(2)

Made up of wholly synthetic detergent. The

first type is usually known as combination bars or combars. These contain 50


percent TFM and 30-35 percent mineral matter like talc and Kaolin. They are
simply structured toilet soaps. Bureau of Indian standards (BIS), warns the
customers of bathing bars. It is important to guard against the removal of the
beneficial skin lipids by bathing bar and over cleaning resulting in defatting of the
skin is undesirable.
High clay content in bathing bar may reduce its solubility and hence increase
its durability. But after bathing with a bathing bar, whole body may be coated with
a white powder, (two-in-one soap + talcum powder) Children and old people can
not tolerate high syndet containing bathing bar, because it would degrease their
skin.

Special processes have been developed by Indian scientists to upgrade


cheaper and easily available raw materials to make good quality toilet soap.
Techniques have been developed to obtain good quality fatty acids for soap
making from fish oil, neem oil and Karanja oil. India is the second largest producer
of castor oil, the first being Brazil. A process was developed in India to convert
castor oil into good quality soap making oil. Textured castor oil is found to be very
good for making transparent soap.
Transparent soap
Transparent soap is a clear soap with high glycerin content often referred to
as glycerin soap. Transparent soap is less drying than opaque soap and can have
additional emollient oils added to it such as Shea butter or jojoba oil. It is basically
partly soap and partly solvent. Sodium hydroxide causes big crystals to form in
soap and that is why the soap becomes opaque. In order to make it transparent, we
have to dissolve the soap in enough solvent to make the crystals so small that light
will feely pass through the soap which makes it look transparent. The solvent used
can be glycerol, alcohol or glycerol alcohol mixture.
Baby soap
Bay soaps are not much different from ordinary soaps, but they are
comparatively of high purity. Babys skin is soft and sensitive. Hence the oil used
for making baby soap should be clean and bleached. No pigments are allowed in
baby soap and fragrance materials added should be bare minimum. Free alkali
content present in baby soap should not exceed 0.05 percent Ordinary soap may
contain rosin and metallic impurities such as nickel. But a bay soap should not
contain such things. Actually baby soap should be cheaper than luxuary soap
because costly perfumes or colouring materials are not present in it.

Medicinal soap
As per many advertisements medicinal soaps are supposed to contain
deodorants antiseptics and some medicines that cure skin diseases. They say that
medicinal soaps are cleansing agents well as antiseptics. Here soap is treated as a
carrier of medicines that is it serves the purpose an ointment or oil. But we should
remember that soap is essentially a cleansing agent. After applying soap to the
body, immediately we used to wash with water, when together with dirt the
medicines if any would also be washed out. We are not giving enough time for the
medicine, to be absorbed by the skin. Then how can they cure skin diseases?
Germicidal soap usually contains the germicide Trichloro carbanilide (TCC) upto 1
percent. When warmed to 60o C, It is converted into chloromine which is toxic to
skin.
Herbal soaps contain some fragrant essential oils. Some soaps contain
Shekakai (Acacia sinuate) which has saponin as an active agent. Saponin is a good
emulsifier. Soft soap: - Soft soaps are usually used in shaving soaps and in liquid
soaps. They are more soluble in water than ordinary soaps. While ordinary soaps
are sodium soaps, soft soaps are potassium soaps.
How Soap works
Dirt and grime usually adhere to skin, clothing and other surfaces because
they are combined with greases and oils body oil, cooking fats, lubricating
greases and a variety of similar substances which act a little like sticky glues.
Since oils are not miscible with water, washing with water alone does little good.
Soap molecule have a split personality. One end is ionic and dissolves in water.
The other end is like a hydrocarbon and dissolves in oils. If we imagine the ionic
end of the molecule as head and hydrocarbon chain as tail, then we can explain
the clearing action of soap clearly. The hydrocarbon tails stick into the oil. The
ionic heads remain in the acqueons phase. In this manner, the oil is broken into

tiny droplets and dispersed throughout the solution. The droplets dont coalerec
because of the repulsions of the charged groups (the caboxl anions) on their
surfaces. The oil and water form an emulsion, with soap acting as an emulsifier.
With the oil no longer gluing it to the surface, the dirt can be removed easily.
This mechanism applies to synthetic detergents also.
Disadvantages of soaps.
For cleaning clothes and for other purposes, soap has been largely replaced
by synthetic detergents. This is because soaps have two rather serious short
comings. One of these is that, in acidic solutions, soaps are converted in to fatty
acids. The fatty acids unlike soap (sodium salt of fatty acids) do not ionise much.
Lacking the split personality, they cant emulsify the oil and dirt that is they do not
exhibit any detergent action. What is more these fatty acids are in soluble in water
and separate as a greasy scum.
The second and more serious disadvantage of soap is that it does not work
very well in hard water. Hard water contains certain metallic ions, particularly
magnesium, calcium and iron ions. The soap anions react with these metal ions, to
form greasy, insoluble curds. These deposits make up the familiar bathtub ring.
They leave the freshly washed hair sticky, and forms kettle fur.
Soap powders and washing powders
Soap powders are not be confused with powdered soaps, which is merely
soap in powdered form. Most soap powders are mixtures of soap and alkali
substances known as builders. Such builders include sodium carbonate, trisodium
phosphate, borax and sodium sulphate. Most frequently used one is sodium
corbonate. Some washing powders also contain a beaching agent, such as sodium
perborate. These usually are called oxygen washes and often contain part of the

word oxygen in the commercial name. As a rule, the cheaper the washing powder,
the larger the proportion of alkali present. The builder is added to soften hard water
and to act as cheap detergent, or cleansing agent. It should be remembered,
however, that the builder is a less efficient cleansing agent than soap.
Synthetic Detergents
Detergent is a cleansing agent. In that sense soap is also a detergent. But the
word detergent usually refers to a synthetic substance other than soap. A detergent
contains an active agent called surfactant, that wets the fabric, emulsifies oily
matter, solubilizes grime and keeps the soil in suspension. This active agent
contains two groups one oil loving lipophilic and the other water loving
hydrophilic.
The first synthetic detergents synthesized were derived from fats by reduction
with hydrogen, followed by reaction with sulphuric acid, and then neutralization.
Example

> Sodium lauryl sulphate (Sodium dodecyl sulphate)


Thus sodium lauryl sulphates are the first such detergents synthesized. But
this process was found to be expensive. Within a few years, cheap synthetic
detergents were produced from petroleum products.
Made largely from a material called aeid clurry which is chemically linear
alkly benzence (LAB). LAB is sulphonated to get linear alkyl benzene sulphonate
(LABS). This is reacted with sodiumhydroxide or sodium carbonate (Sodaash) to

form its sodium salt soluble in water. The products for use in homes and
commercial laundries usually contain much more than LABS molecules. The
LABS is called a surface active agent or surfactant. In addition to the LABS
modern detergent formulations contain a number of other substances to improve
detergency, to bleach, to lessen redeposition of dirt, to brighten, or simply to
reduce the cost of the formulation.

An substance added to a surfactant to increase its detergency is called a


builder. Common builders are the Phosphates. An example is sodium tripoly
phosphates (Na3 P3 O10). It ties up Ca2+ and Mg 2+ in soluble complexes this
softening water. It also produces a mild alkalinity, proving a favourable
environment for detergent action. Other builders and fillers added include soda ash,
sodium silicate, sodium chloride, sodium sulphate and Zeolite (special form of clay
- hydrated sodium aluminium silicate.

Detergents are graded on the basis of their active matter, and poly phosphate
content. Detergents can be used in hard water, but removal from fabrics requires a
to lot of rincing. Detergents can be used in cold and hot water as well as acidie and
alkaline conditions.

Cotton fabrics can be washed with detergents heavy with phosphates and
soda a sh. Wool, nylon and silk fabrics should be washed with detergents, which
have less alkali, less phosphates, and less soda ash.
Heavy duty detergent powders are two types. one suitable for handwashing
and the other for machine washing. Detergents used for hand washing should give
copious lather. That would satisfy the aesthelic sense of the customer. But the fact

is that the amount of form is not a measure of the effectiveness of the detergent.
however a small amount of foam is necessary to trap the dirt and carry it away
during rinsing. But detergents used in washing machine should not produce much
foam, because it may damage the machine parts, especially of the front loading
machines.
The optimum concentration of active matter is found to be0.05 percent or
half gram per litre or 5 gram in ten liters. 50 g of a popular low priced detergent
powder is needed in 10 litres of water for optimim economy and efficiency.
Preference of sodium triploy phosphate in detergent increases its clean ring
powder. For localized cleaning it is better to use detergent bar.

TYPICAL COMPOSITION DIFFERENT TYPES A DETERGENT


POWDERS AND DETERGENTS BARS.

HIGH
MEDIUM
LOW
HIGHT
LOW
PRICED PRICED PRICED PRICED PRICED
POWDER POWDER POWDER
BAR
BAR
Active matter

15-18%

11-14%

8-10%

18-20

12-15

Phosphates/Zeolites

15-20%

5-8%

Nil

10-15

5-15

Soddash

5-10%

12-20%

30-70%

Nil

5-15

Sodium silicate

4-5%

15-30%

Nil

Sodium Sulphate

24-40%

23-36%

3-5%

2-3

2-3

Sodium Chloride

Nil

Nil

7-50%

5-10

10-20

Clay

Nil

15-20%

10-20%

30-50

40-60

8-10%

10-15%

15-20%

5-10

10-12

10-15

5-10

1-3

0-2

Moisture
Starch/
Wax

POWDER

GREADE PERCENTAGE
ACTIVE
MATTER
1

19

MAXIMUM
PERCENTAGE OF
SODIM CABONATE
ALLOWED.
30

16

40

15

50

12

60

Health and Detergents


The basic function of a detergent is to remove dirt. In our country most of
the people are washing their clothes with their hands. The detergent which removes
the dirt and grime from the clothes also degreases the skin while washing the
clothes. Thus natural oils from the skin are removed which may lead to certain skin
diseases. Alkaline materials which are also present in the detergent powders and
bars will intensity this. LABS can penetrate, the epidermis causing irritation of the
skin. More over the alkaline builders and fillers added to the detergents are also
harmful to the sensitive skin. If the clothes are not washed very well with water,
the residual detergent sticking to the cloth also may irritate the skin. Metallic
impurities like nickel present in the detergent powders or cakes are also harmful.
Alpha olefin sulphonate (AOS) is now days used as detergent instead of LABS.
Some time AOS is mixed with sultones which are also good surfactants. Sultones
are very sensitive to skin. One advantage of AOS is that it is completely
biodegradable.

Spray dried and Drymix powders

The grains of spray dried detergent powder are hollow globules. They look like
beautiful little pearls. The powder is freed flowing and very well soluble in water.
Since it is very attractive customers prefer it even though it is bit costly.
Drymix detergents are made by mixing the pre-dried ingredients throughly either
manually or using a mixer. The density of this powder is higher than that of spray
dried powder. There is not much difference between them in detergent action. But
drymix powder tend to cake on contact with moisture.

Compact detergents
Concentrated or compact detergents contain about 25 percent of active matter; and
the rest consists of builders and fillers. Now a days in order to reduce packaging
cost, compact detergents containing 40 to 60 percent of active matter have been
introduced by leading companies.

Detergents and environment


Use of phosphates, enzymes, bleachers, and brightening agents in detergents is a
subject of debate among environmentalists. Even though phosphates are perfect
builders they suffer from one overwhelming defect: they are superb, nutrients for
the algae and other small plants and grow on the surfaces of lakes and streams.
Algae, nourished by a steady supply of phosphates, can cover the surface of body
of water and prevant atmosheric oxygen from reaching the marine life below the
surface. The resulting death of fish and other aquatic animals sometimes occurring
on a large scal in lakes and rivers covered by algae, has led many countries to ban
the use of phosphates as detergent builders. This type of water pollution is known

as Eutrophieation. In india 80 percent of the detergents marketed are phosphate


free, hence eutrophieation from detergents does not happen. The most promising
substitute for phosphates is a class of compounds of aluminium, silicon and oxygen
known as zeolites.
Chemical composition of a detergent does not correctly reveal its cleaning
capacity. For a practical and realistic evaluation, it is necessary to determine the
actual performance of detergents. Detergency is measured by reflectance. Infact
there is not much difference in detergency between low grade and high grade
detergents.
All the surfactants discussed so far, including soap are anionic surfactants;
The working part of the molecule is an anion with a nonpolar part and anionic end.
Some liquid detergents contain nonionic surfactants. Examples are alcohol
ethoxylates and alkyl phenol ethoxylates. The several oxygen atoms, by their
attraction for water molecules, make that end of the molecule water soluble.
Nonionic surfactants are great for removing oily soil from fabrics. They are more
soluble in cold water than in hot water.
There are eat ionic surfactants also, in which the working part of the
molecule is a action. The most common of these are called quaternary ammonium
salts.

An

example

of

such

an

eat

ionic

surfactant

is

hexadecyl

timethylammoniumchloride. These are not very good detergents, but they have a
degree of germicidal action. Sometimes they are used along with nonionic
surfactants, as cleaners and disinfectants in good and dairy industries. Eat ionies
cannot be used with anionic surfactants.
Of all the house hold chemicals, the detergents and related cleaning
compounds make up the greatest volume. Extensive use of these chemicals has led
to an increasing number of health and environmental problems. Hence care should

be taken to use them in homes with proper regard to the directions or precautions
given on their labels. It would be nice if every one knew a lot of chemistry.